WO1997002307A1 - Polymer material, process for its production and use thereof - Google Patents

Abstract

The invention concerns a polymer material based on renewable raw materials and containing a reaction product comprising 10 to 90 mass % of a triglyceride having at least two epoxy and/or aziridine groups, and 5 to 90 mass % of a polycarboxylic acid anhydride with 0.01 to 20 mass % of a polycarboxylic acid.

Description

 Polymer material,

 Process for its production and its use The invention relates to a polymer material on the

Basis of renewable raw materials and a process for the production of this material and its use.

Organic plastics, which are used on an industrial scale today, are obtained almost exclusively on a petrochemical basis. For example, in the construction of furniture and in the construction industry, wood-based materials are used that are UF, MUF, PF or, more rarely, PUR-bound. Cover plates, end pieces, cable ducts, etc. mostly consist of polyvinyl chloride (PVC).

In the field of windows, plastic windows with frames made of PVC are also used in large numbers. PVC as a material for such components, however, has decisive disadvantages. For one thing, recycling is not yet satisfactory Lend solution, on the other hand, PVC develops dangerous gases in the event of fire. Cladding elements for machines and devices, high-quality molded articles are often made of PF, MF, EP or UP reinforced fiber materials or mats, for example in the

Automotive industry can be used. In the course of the increasing CO2 discussion and a possible possible global climate change, there is a great need for new, largely CO2-neutral plastics that meet the high requirement profiles of currently used plastics on a petrochemical basis and could partially replace them. Such polymer materials are expediently obtained from starting materials on the basis of renewable raw materials.

Binders or binder combinations, some of which also contain renewable raw materials, have already become known from the prior art. These developments relate in particular to the

Polyurethane area. It is known from US Pat. No. 458,2891 to implement castor oil, that is to say a renewable raw material, with polyisocyanate and an inorganic filler.

EP 01 51 585 discloses a two-component polyurethane adhesive system in which ring-opening products of epoxidized fatty alcohols, fatty acid esters (in particular triglycerides) or fatty acid amides with alcohol are used as the oleochemical polyol. It is also known to use epoxidized triglycerides as plasticizers. Such a method is described, for example, in PCT / EP94 / 02284. From US 35 78 633 a method for curing polyepoxides with polycarboxylic anhydride using special alkali salts of selected carboxylic acids is known. Thereafter, only polyepoxides with more than one vicinal epoxy group per

Molecule used. However, the polymers obtained according to this document have the disadvantage that, on the one hand, they start from physiologically questionable starting substances (e.g. lithium salts) and, on the other hand, that the polymers obtained do not have the required strengths. This is obviously due to the fact that, according to the US patent, a basic reaction takes place which supports the crosslinking of external epoxy groups, but which are in no way present in epoxidized triclycerides.

DE 41 35 664 discloses polymer products which are produced from epoxidized triglycerides and partial esters of polycarboxylic acids with at least two free carboxylic acid groups and with hydrophobizing agents. According to DE 41 35 664, however, elastic coating compositions with increased water resistance are obtained, which likewise do not have satisfactory properties with regard to the strength and the range of variation of the polymer system.

Proceeding from this, it is therefore the object of the present invention to provide a new type of material which is based on renewable raw materials and which leads to polymer materials which, in terms of their strength, permit a wide range of applications.

The object is achieved with respect to the polymer material by the characterizing features of claim 1, solved with respect to the method by the characterizing features of claims 15 and 16. The subclaims show advantageous developments. According to the invention, a polymer material is thus proposed which essentially contains a reaction product of three components, namely 10-90% by mass of a triglyceride, 5-90% by mass of a polycarboxylic acid anhydride with 0.01-20% by mass of a polycarboxylic acid. The applicant was able to show that, surprisingly, polymer materials which contain a reaction product in the manner described above have surprising properties with regard to the strength and the range of variation of the properties of the material.

It is crucial for the material according to the application that polycarboxylic anhydrides are used which act as crosslinking agents, so that the crosslinking density of the polymer obtained is decisively increased. in the

The result of this is hard polymers.

The main components of the reaction product are thus epoxidized triglycerides and polycarboxylic anhydrides, which are cross-linked. The crosslinking reaction is started by adding small amounts of polycarboxylic acid (0.01 to 20% by mass). The polycarboxylic acid thus obviously has the advantageous function of an initiator for the internal epoxy groups of the triglycerides.

The use of polycarboxylic acid anhydrides therefore crosslinks the neighboring OH groups formed through the epoxy ring opening in the form of an addition reaction. The Polycarbonsäureanhy The resulting free carboxylic acid group thus obviously opens another epoxy ring, whereby an adjacent OH group is also obtained, which reacts with an additional carboxylic anhydride group with further addition. The reaction is started when an epoxy ring has been opened and the neighboring OH group has formed. This initiation of the crosslinking takes place by adding small amounts of polycarboxylic acid. It is therefore essential that the epoxy group is opened as the start of the reaction. A possible reaction sequence is shown schematically below.

Im Unterschied zum Stand der Technik mit den Vernetzungen mit reinen Polycarbonsäuren reagieren die gebildeten Hydroxygruppen unter Polyaddition mit dem Polycarbonsäureanhydrid. Dies konnte auch durch DSC und IR-Untersuchungen belegt werden.

In contrast to the prior art with crosslinking with pure polycarboxylic acids, the hydroxy groups formed react with the polycarboxylic anhydride with polyaddition. This could also be proven by DSC and IR investigations.

It is therefore essential for the polymer material according to the application that it contains a reaction product that consists of 10-90% by mass of a triglyceride and 5-90% by mass of a carboxylic anhydride, the

Reaction can be initiated by small amounts of polycarboxylic acid (0.01-20% by mass). It is preferred if the reaction product contains 35-70% by mass of a triglyceride and 10-60% of the polycarboxylic anhydride and 0.05-10% by mass of the polycarboxylic acid.

Examples of epoxidized triglycerides which can be used in the polymer material to produce the reaction product according to the invention are soybean oil, linseed oil, perilla oil, tung oil, oiticica oil, safflower oil, poppy oil, hemp oil, cottonseed oil, sunflower oil, rapeseed oil, triglycerides from Euphorbia waxes such as Euphorbia Iagascae oil and higholeic triglycerides such as higholeic sunflower oil or Euphorbia-Iathyris oil, peanut oil, olive oil, olive kernel oil, almond oil, kapok oil, hazelnut oil, apricot kernel oil, beech nut oil, lupine oil, corn oil, sesame oil, ricinese oil, l such as herring oil and sardine oil or menhaden oil, whale oil and triglycerides with a high saturated fatty acid content, which is subsequently converted into an unsaturated state, for example by dehydrogenation, or mixtures thereof. Because of the reaction with the hydroxyl groups, it is possible, in addition to epoxidized triglycerides, to also use hydroxylated triglycerides as a further component to use. Such hydroxylated triglycerides are, for example, hydroxylated high oleic or castor oil. In this way, the physical properties of the polymers can be largely modified. It is essential, however, that epoxidized triglycerides are always present, otherwise chain termination will occur. It is also possible to use triglycerides with aziridine groups. Different synthetic routes are known for the preparation of aziridines. One production route is the cycloaddition of, for example, carbenes to azomethines (Breitmaier E., G. Jung, Org. Chemie Vol. 1, E. Thieme Berlag, Stuttgart) or of nitrenes to olefins. A synthesis by reduction of α-chloronitriles or oximes with LiAlH ₄ is also possible (Bull. Chem. Soc. Jpn. 40, 432 (1967) and

Tetrahedro 24, 3681 (1968).

In the case of the polycarboxylic acid anhydrides, preference is given to those which have a cyclic backbone, ie polycarboxylic acid anhydrides which are prepared from cyclic polycarboxylic acids having at least two free carboxylic acid groups. Examples of this are cyclohexane dicarboxylic anhydride, cyclohexenedicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, Hemimellithsäureanhydrid, pyromellitic anhydride, 2,3-naphthalic anhydride, 1,2 Cyclopendandicarbonsäureanhydrid, 1,2 Cyclobutandicarbonsäureanhydrid, Chinolinsäureanhydrid, Norbornendicar- bonsäureanhydrid (NADICAN) and the methyl-substituted compounds MNA, Pinsäureanhydrid, Norpinsäureanhydrid , Truxilic anhydride, perylene 1,2-dicarboxylic anhydride, caronic anhydride, narcamphanic dicarboxylic anhydride, isatoic anhydride, camphoric anhydride, 1,8-naphthalic anhydride, diphenic anhydride, o-carboxyphenylacetic anhydride, 1,4,5,8- Naphthalene acarboxylic anhydride or mixtures thereof.

Polycarboxylic acid anhydrides from open-chain di- and polycarboxylic acids with at least two free carboxylic acid groups, such as e.g. Aconitic anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride, tartaric anhydride, diglycolic anhydride, ethylenediamine acetic anhydride or mixtures thereof.

In the initiators used according to the invention, i.e. in the case of the polycarboxylic acids, the di- and tricarboxylic acids are preferred. Examples of these are citric acid derivatives, polymerized tall oils, azelaic acid, gallic acid, di- or polymerized resin acids, di- or polymerized anacardic acid, also cashew nut shell liquid, polyuronic acids, polyalginic acids, mellitic acid, trimesic acid, aromatic di- and polycarboxylic acids such as e.g. Phthalic acid, trimellitic acid,

Hemimellitic acid, pyromellitic acid and their aromatically substituted derivatives such as hydroxy or alkyl phthalic acid, unsaturated cyclic di- and polycarboxylic acids such as norpic acid, heterocyclic di- and polycarboxylic acids such as loiponic acid or cincholoiponic acid, bicyclic di- and polycarboxylic acids such as norbornane dicarboxylic acid and polycarboxylic acids, such as malonic acid and its longer-chain homologues, and their substituted compounds, such as, for example, hydroxy and keto, di- and polycarboxylic acids, pectic acids, humic acids, polymeric cashew nut-shell liquid with at least two free carboxylic acid groups in the molecule or mixtures thereof. Another preferred embodiment of the invention proposes that the polymer material contains a reaction product which was produced from the starting components described above, but additionally with a catalyst. The catalyst can be added in a quantitative ratio of 0.01-10 mass%, preferably 0.05 to 5 mass%. In principle, all compounds which serve to accelerate the crosslinking of epoxy resins can be used as catalysts. Examples include tertiary amines such as N, N'-benzyldimethylaniline, imidazole and its derivatives, alcohols, phenols and their substituted compounds, hydroxycarboxylic acids such as lactic acid or solicylic acid, organometallic compounds such as triethanolamine titanate, di-n-butyltin laurate, Lewis acids, especially boron trifluoride, aluminum trichloride and their amine complex compounds, Lewis bases, especially alcoholates, multifunctional mercapto compounds and thioacids as well as organophosphorus compounds, especially triphenylphosphite, trisnonylphenylphosphite and bis-ß-chloroethylphosphite, bicyclic amines such as [2.2.2] diazabicyclidinec, diazabicyclidinec Alkali and alkaline earth hydroxides, Grinard compounds or mixtures thereof.

It should be particularly emphasized that the polymer material according to the invention can consist exclusively of the reaction product, as described above, or, depending on the requirement profile, additionally one

Can contain filler or a flame retardant. If the polymer material contains only one reaction product and filler, it is preferred that it contains 2-98% by mass of the reaction product and 98-2% by mass of the filler. Especially it is preferred if the polymer material contains 6-90% by mass of the reaction product and 10-94% by mass of the filler. Particularly preferred examples of fillers are organic fillers based on cellulose-containing materials such as wood flour, sawdust or wood waste, rice husks, straw and flax fibers based on proteins, especially sheep's wool, and inorganic fillers based on silicates and carbonates such as sand, quartz, corundum , Silicon carbide and glass fibers, or mixtures thereof. The polymer material according to the invention can also contain up to 50% by mass of a flame retardant. Preferred flame retardants are: aluminum hydroxide, halogen,

Antimony, bismuth, boron or phosphorus compounds, silicate compounds or mixtures thereof.

In the production of the material according to the preferred embodiment with the filler, the procedure can be such that firstly a mixture of the starting components, i.e. of the triglyceride of the polycarboxylic acid anhydride and the carboxylic acid is prepared, and then this mixture is then prepolymerized to a viscosity of 0.2-20,000 CPS at 20 ° C-200 ° C and then the filler is added. Following this, curing may also take place after shaping, if necessary under pressure. However, it is also possible to mix all the additives and then carry out the prepolymerization.

On the other hand, it can also be done in such a way that all starting materials, ie the triglycerides, the polycarboxylic anhydrides and the carboxylic acids and, if appropriate, the other additives such as fillers and / or flame retardants are mixed, and then the curing then takes place at elevated temperature and temperature and pressure.

Curing can take place in a range from> 20 ° C to 200 ° C at a pressure of 1 bar to 100 bar. The duration of the curing depends on the temperature, the pressure and, if applicable, the catalyst added. The curing time can range from 10 seconds to 24 hours. The preferred temperature range is 50-150 ° C.

The polymer material according to the invention can also be infiltrated in nonwovens or mats. This enables fiber-reinforced molded parts to be produced.

With the method according to the invention, the mixture obtained can be individually put into molds and pressed, or continuous production can be carried out. The continuous production can also be done by extrusion or hot rolling.

After curing, the reaction mixture forms a closed and extremely smooth surface, the plastic dissolution, i.e. the size of geometric figures that can still be plasticized is very high. The finest filigree patterns are reproduced very precisely by the material.

The material according to the invention is particularly characterized in that it is toxicologically harmless and therefore does not have the disadvantages of PVC and / or other comparable materials, such as those based on polyurethane. It should be mentioned that the Novel material can have mechanical properties similar to PVC, EP or PES. These material variants are rigidly elastic and of high strength. Highly filled cellulose-containing polymer materials according to the invention, which were obtained by pressing or extrusion, have high mechanical strengths. With mechanical point loading, such as occurs when fastening wood screws or inserting wooden nails, this remains

Preserve the structure of the surrounding material. Cracking, as can occur with wood, for example, is not observed. The material can be machined easily. When sawing or milling, no tearing of the interfaces or even flaking off of smaller sections can be observed.

Additional portions of hydroxylated triglycerides can be used to obtain moldings which have a partially plastic behavior at room temperature and at the same time have excellent tear strength. Depending on

Degree of crosslinking, which can in principle be influenced by the composition of the starting components, moldings can be obtained which permit hot forming of the polymer material body. In particular, the incorporation of aluminum hydroxide in fire tests shows a noticeable improvement in fire behavior. The installation of aluminum hydroxide and the associated elimination of water prevent the flames from attacking directly. The fire protection class BS according to DIN 4102 is thus fulfilled.

Numerous tests have also shown that there is no noticeable water absorption in the material according to the invention, highly filled with cellulose For this purpose, pellets were immersed in water over a longer period of time. After 80 hours, no significant amount of water was absorbed by the material. No physical and chemical changes could be observed on the material.

The invention is illustrated by the following examples: Example 1

53.5% by mass of epoxidized linseed oil with an oxygen content of 9% by mass are mixed with 42.8% by mass of camphoric anhydride and 2.7% by mass of a mixture of di- and trimeric abietic acid. This

Mixture is homogenized with 1 mass% of a 50% ethanolic quinuclidine solution. 10% by mass of this mixture are mixed with 90% by mass of straw and pressed at a pressure of 15 bar and a temperature of 180 ° C. for 10 minutes. The fiberboard obtained has a physical density of 0.62

[g / cm ³ ], is characterized by high-quality mechanical properties and has excellent water resistance. It can be used as fiberboard material in the construction and furniture industries.

Example 2 80 parts by weight of epoxidized perilla oil with an oxygen content of 8% by weight are mixed with 16 parts by weight of pyromellitic dianhydride and 4% by weight of a trimerized fatty acid. 30% by mass of this mixture is made up to 70% by mass of a jute-hemp Nonwoven applied so that the nonwoven is homogeneously wetted. The infiltrated fiber mat is then pressed at a pressure of 10 bar and a temperature of 170 ° C for 10 minutes. The fiber product obtained has a high elasticity,

Breaking strength and water resistance. It can be used in many areas in which plastic-reinforced fibers or fiber-reinforced plastics are used, such as fiber-reinforced formwork and molded parts or cladding elements.

Example 3

42.9% by mass of epoxidized soybean oil with an oxygen content of 6.5% by mass are mixed with 21.5% by mass of a hydroxylated high oleic oil. 34.3% by mass of norbornene dicarboxylic acid anhydride and 1.3% by mass of a 5% methanolic DABCO solution are added to this mixture. The mixture is homogenized and then at a temperature of

140 ° C networked within 15 minutes. The product obtained is transparent, plastically deformable and has a high tear resistance. This product can be used to coat materials and components that need to be plastically deformable, e.g. electrical cables.

Example 4 72.7 mass% epoxidized hemp oil with an oxygen content of 10.5 mass% is mixed with 27.3 mass% trimellitic anhydride. 8% by mass of this mixture are mixed with 92% by mass of dried spelled husks and pressed at a pressure of 15 bar and a temperature of 170 ° C. for 8 minutes. The fiberboard obtained has a physical density of 0.88 [g / cm ³ ], is characterized by high water resistance and excellent mechanical strength and can be used as a fiberboard in the construction and furniture industries.

Example 5

54.7% by mass of epoxidized linseed oil with an oxygen content of 9.6% by mass becomes 43.7% by mass.

Tetrahydrophthalic anhydride and 1.1 mass% adipic acid mixed. This mixture is homogenized with 0.5% by mass of DBN and crosslinked at 145 ° C. within 5 minutes to form a hard, transparent shaped body. The material obtained is water and boiling water resistant (see Fig. 1 and 2) and has high mechanical strength. The material can be heated up to 300 ° C without decomposition. For example, suitable as a cladding element for devices and machines of all kinds.

Example 6

60% by mass of epoxidized soybean oil with an oxygen content of 6.5% by mass are mixed with 36% by mass of 1.2 cyclohexanedicarboxylic acid anhydride and 1.1% by mass of dimerized rosin with an acid number of 154. The mixture is homogenized with a 50% butanolic imidazole solution and crosslinked at 140 ° C. within 10 minutes. The polymer material obtained is transparent, is characterized by high water resistance and can be hot formed at a temperature of approx. 90 ° C. Below this temperature it has high mechanical strength. Example 7

69.9% by mass of a higholeic oil containing aziridine groups from Euphorbia Lathyris with a nitrogen content of 4.3% by mass are mixed with 28% by mass of phthalic anhydride, 1.5% by mass of sebacic acid and 0.6% by mass of an isopropanolic quinuclidine solution . The mixture is crosslinked at 145 ° C over a period of 5 minutes to form a hard-elastic, transparent polymer material that has high water resistance and abrasion resistance.

Example 8 51.5% by mass of an epoxidized tung oil with a

Oxygen content of 10.5 mass% are mixed with 45.5 mass% camphoric anhydride and 2.5 mass% of a 70% ethanolic citric acid solution. 0.5% by mass of DABCO are added to this mixture and the mixture is homogenized. 30% by mass of this mixture are applied to 70% by mass of a dry coconut fiber fleece, so that the fibers are homogeneously infiltrated with the reactive mixture. The infiltrated coconut fiber is then preheated at 130 ° C for 20 minutes. The reactive mixture reacts to a prepolymer with a viscosity of approximately 10,000 [mPas]. The pretreated fleece is then placed in a mold and pressed at a temperature of 160 ° C. for 1 minute at 15 bar. The fiber product obtained has a high mechanical strength, is very water-resistant and temperature-resistant. It can be used in areas where plastic-reinforced nonwovens or fiber-reinforced plastics are used. Example 9

A mixture of 61.6% by mass of epoxidized linseed oil with an oxygen content of 9.6% by mass and 15.4% by mass of epoxidized sardine oil with an oxygen content of 10.5% by mass are mixed with 19.2 parts by weight of pyromellitic dianhydride and 3, 8 mass% trimerized fatty acid mixed. 25% by mass of this mixture are homogenized with 75% by mass of wood flour with an average fiber length of 300 μm. The wetted powder is then processed with a RAM extruder at 160 ° C and a pressure of 40 bar into continuous molded parts. The contained products have a high mechanical stability and are characterized by an excellent water resistance.

Example 10 53.2% by mass of an epoxidized safflower oil with a

Oxygen content of 9% by mass are mixed with 10% by mass of aconitic anhydride, 32.5% by mass of methylnorbornene dicarboxylic acid anhydride and 2.6% by mass of dimerized anacardic acid. 1.7% by mass of a propanolic DABCO solution are added to this mixture and the mixture is then homogenized. 10% by mass of this mixture are mixed with 90% by mass of dried and ground rice husks with a medium grain size of 0.5 mm until a homogeneously wetted powder is obtained. This mixture is then pressed at a temperature of 130 ° C for 15 minutes at a pressure of 15 bar. The material obtained has a physical density of 0.9 [g / cm ³ ] and can be machined. This material is suitable wherever medium density fibreboard (MDF) is used.

Example 11

50.5% by mass of epoxidized linseed oil are mixed with 42.5% by mass of tetrahydrophthalic anhydride and 2.5% by mass of trimerized abietic acid. This mixture is homogenized with 1.8% by mass of a 50% isobutanolic quinuclidine solution. 30 mass% of this

Mixture with 35 mass% heavy spar, 5 mass% of a pigment such as Homogenized rutile and 30% by mass of a mixture of muscuvite, chlorite and quartz flour. The mixture is then crosslinked in a mold at a pressure of 30 bar and a temperature of 140 ° C. within 8 minutes to give hard-elastic, thermoset molded articles which have high resistance to water and cooking water and high mechanical strength. The material can e.g. can be used as a cladding element for devices and machines of various types.

Claims

claims 1. Polymer material based on renewable raw materials, containing a reaction product of 10-90 mass% of a triclyceride with at least 2 epoxy and / or aziridine groups and 5-90 mass% of a polycarboxylic acid anhydride with 0.01-20 mass% of a polycarboxylic acid . 2. polymer material according to claim l,  characterized in that the epoxidized triclycerides from soybean oil, linseed oil, perilla oil, tung oil, oiticica oil, safflower oil, poppy oil, hemp oil, cottonseed oil, sunflower oil, rapeseed oil, triglycerides from Euphorbia waxes such as e.g. EuphorbiaIagascae oil and high oleic triglycerides such as higholeic sunflower oil or Euphorbia-Iathyris oil, peanut oil, olive oil, olive kernel oil, almond oil, kapok oil, hazelnut oil, apricot kernel oil, beech nut oil, lupine oil, corn oil, sesame oil, grape seed oil, Lallemantia oil, castor oil, or herring oil, herring oil, or herring oil , Whale oil and triglycerides with a high saturated fatty acid content, which can be added afterwards by dehydration to an unsaturated state  is transferred, or mixtures thereof are selected. 3. polymer material according to claim 1 or 2, characterized in that the epoxidized triglycerides additionally contain hydroxylated triglycerides such as castor oil. 4. Polymer material according to at least one of the  Claims 1 to 3,  characterized in that the polycarboxylic anhydrides are prepared from cyclic polycarboxylic acids with at least 2 free carboxylic acid groups. 5. polymer material according to claim 4,  characterized in that the polycarboxylic acid anhydrides are selected from cyclohexane dicarboxylic acid anhydride, cyclohexane dicarboxylic acid anhydride, phthalic acid anhydride, trimellitic acid anhydride, hemimellitic acid anhydride, pyromellitic acid anhydride, 2,3-naphthalic acid anhydride, 1,2 cyclopendanedicarbonic acid dicarbonic acid dicarbonic acid dicarbonic acid dicarbonic acid dicarbonic acid dicarbonic acid dicarbonic acid dicarbonic acid dicarbonic acid dicarboxylic acid -substituted compounds MNA, pinic anhydride, norpic anhydride, truxilic anhydride, perylene 1,2-dicarboxylic anhydride, Caronic anhydride, narcamphanedicarboxylic anhydride, isatoic anhydride, camphoric anhydride, 1,8-naphthalic anhydride, diphenic anhydride, o-carboxyphenylacetic anhydride, 1,4,5,8-naphthaleneacarboxylic anhydride, or mixtures thereof. 6. Polymer material according to at least one of the  Claims 1 to 3, characterized in that the polycarboxylic anhydrides are prepared from open-chain di- and polycarboxylic acids with at least 2 free carboxylic acid groups. 7. polymer material according to claim 6,  characterized in that the polycarboxylic anhydrides are selected from aconitic anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride, tartaric anhydride, Diglycolic anhydride, ethylenediamine acetic anhydride or mixtures thereof. 8. Polymer material according to at least one of the  Claims 1 to 7,  characterized in that a di- or tricarboxylic acid is used as the polycarboxylic acid. 9. polymer material according to claim 8,  characterized in that the polycarboxylic acid is selected from citric acid derivatives, polymerized tall oils, azelaic acid, gallic acid, di- or polymerized resin acids, di- or polymerized anacardic acid, also cashew nut shell liquid, polyuronic acids, polyalginic acids, Mellitic acid, trimesic acid, aromatic di- and polycarboxylic acids such as Phthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid and their aromatically substituted derivatives such as e.g. Hydroxy or alkyl phthalic acid, unsaturated cyclic di- and polycarboxylic acids such as e.g. Norpinic acid, heterocyclic di- and polycarboxylic acids such as e.g. Loiponic acid or cincho-loiponic acid, bicyclic di- and polycarboxylic acids such as e.g. Norbornane dicarboxylic acids, open-chain di- and polycarboxylic acids, e.g. Malonic acid and its longer chain homologues as well as their substituted compounds such as e.g. Hydroxy and keto, di and polycarboxylic acids, pectic acids, humic acids, polymeric cashew Nut-Shell-Liquid with at least two free carboxylic acid groups in the molecule, or mixtures thereof can be used. 10. Polymer material according to at least one of the  Claims 1 to 9,  characterized in that it contains 2-98% by mass of a reaction product according to claim 1 and 98-2% by mass of a filler. 11. Polymer material according to at least one of the  Claims 1 to 10,  characterized in that the filler is selected from the group of organic fillers based on cellulose-containing materials such as wood flour, sawdust or wood waste, rice husks, straw and flax fibers based on proteins, especially sheep's wool, and inorganic fillers based on silicates and carbonates such as sand, quartz, corundum, silicon carbide and glass fibers, or mixtures thereof. 12. Polymer material according to at least one of the  Claims 1 to 11,  characterized in that 0.01-10% by mass of a catalyst are added in the preparation of the reaction product. 13. Polymer material according to claim 12, characterized in that the catalyst is selected from tertiary amines, such as N, N'-benzyldimenthylaniline, imidazole and its derivatives, alcohols, phenols and their substituted compounds, hydroxycarboxylic acids such as lactic acid or solicylic acid, organometallic compounds such as triethanolamine titanate, di-n-butyltin laurate, Lewis acids, especially boron trifluoride, aluminum trichloride and their amine complex compounds, Lewis bases, especially alcoholates, multifunctional mercapto compounds and thiosacids, and organophosphorus compounds, especially triphenylnophosphate, especially triphenylphosphonyl bis -ß-chloroethylphosphite, bicyclic amines such as [2.2.2] diazabicyclooctane, quinuclidine or diazabicycloundecene, alkali and alkaline earth metal hydroxides, Grinard compounds or mixtures thereof. 14. Polymer material according to at least one of the  Claims 1 to 13,  characterized in that it additionally contains a flame retardant selected from the group consisting of aluminum hydroxide, halogen, antimony, bismuth, boron or phosphorus compounds, silicate compounds or mixtures thereof. 15. A process for the preparation of the polymer material according to at least one of claims 1 to 14, characterized in that the triglyceride, the polycarboxylic anhydride, the polycarboxylic acid and, if appropriate, the further additives, such as fillers and / or catalyst and / or flame retardant, are mixed and then the Curing takes place. 16. A process for the preparation of the polymer material according to at least one of claims 1 to 14, characterized in that the triglyceride, the polycarboxylic anhydride and the polycarboxylic acid and optionally the catalyst up to a viscosity of 0.2 - 20,000 CPS are pre-crosslinked at 20 ° C - 200 ° C and then the filler and / or the flame retardant are added and the curing then takes place. 17. The method according to claim 15 and 16,  characterized in that the curing at a temperature in the range from> 20 ° C to 200 ° C and at a pressure of 1 bar to 100 bar for a time in the range from 10 seconds to Is carried out 24 hours. 18. Use of the polymer material according to at least one of claims 1 to 14,  in prefabricated room division systems, as Material substitute for plastic and metal frames, as a lacquered rail and cladding element, as a profile material, as a sealing material, highly abrasion-resistant coatings and moldings, as a crack-bridging protective skin, non-slip coatings, electrically insulating or conductive materials, tribologically applicable films, underwater ship coatings, vortex sintering systems for stressed equipment and molded parts, molded elements as infiltrated fibers and fiber mats, chipboard, MDF and hardboard substitutes in the construction and furniture industry, endless profiles.